Back to EveryPatent.com
United States Patent |
5,319,042
|
Bell
|
*
June 7, 1994
|
Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts
Abstract
This invention relates to a two component catalyst system for the
polymerization of metathesis polymerizable cycloolefins, comprising (a) a
tungsten compound of the formula WOX.sub.4-x (OAr).sub.x where X is
chlorine, bromine or fluorine, Ar is a hindered phenyl ring having 1-5
specified substituents and x = 1, 2 or 3; and (b) an activator compound.
Among the preferred molecules or groups that are substituted on the phenyl
ring of the tungsten compound are phenyl, chlorine, bromine, methoxy and
isopropyl groups. Ar can also represent a multi-substituted phenyl group
such as 2,4-dichloro-6-methylphenyl.
Inventors:
|
Bell; Andrew (West Grove, PA)
|
Assignee:
|
Hercules Incorporated (Wilmington, DE)
|
[*] Notice: |
The portion of the term of this patent subsequent to January 21, 2009
has been disclaimed. |
Appl. No.:
|
780692 |
Filed:
|
October 18, 1991 |
Current U.S. Class: |
526/169; 264/328.2; 502/102; 502/117; 526/77; 526/126; 526/128; 526/139; 526/141; 526/142; 526/161; 526/163; 526/166; 526/281; 526/282; 526/283 |
Intern'l Class: |
C08F 004/78; C08G 061/08 |
Field of Search: |
526/169,283,161,163,166,281,282,77,139,141,142
502/117
|
References Cited
U.S. Patent Documents
4239874 | Dec., 1980 | Ofstead et al. | 526/143.
|
4550216 | Oct., 1985 | Basset et al. | 526/283.
|
4727125 | Feb., 1988 | Nelson | 526/141.
|
4729976 | Mar., 1988 | Sjardijn et al. | 502/102.
|
4748216 | May., 1988 | Tom | 526/77.
|
4810762 | Mar., 1989 | Sjardijn et al. | 526/166.
|
4861848 | Aug., 1989 | Basset et al. | 526/283.
|
4994426 | Feb., 1991 | Sjardijn et al. | 502/158.
|
5028672 | Jul., 1991 | Sjardijn et al. | 526/128.
|
5071812 | Dec., 1991 | Kelsey | 502/164.
|
5081208 | Jan., 1992 | Sjardijn | 526/166.
|
5082909 | Jan., 1992 | Bell | 526/169.
|
5093441 | Mar., 1992 | Sjardijn et al. | 526/126.
|
5095082 | Mar., 1992 | Kelsey | 526/282.
|
Foreign Patent Documents |
266587 | May., 1988 | EP.
| |
294620 | Dec., 1988 | EP.
| |
360262 | Mar., 1990 | EP.
| |
374997 | Jun., 1990 | EP.
| |
376198 | Jul., 1990 | EP.
| |
376199 | Jul., 1990 | EP.
| |
Primary Examiner: Teskin; Fred
Attorney, Agent or Firm: Patterson; Joanne W., Goldberg; Mark
Parent Case Text
This is a Continuation in-Part of application Ser. No. 07/596,265, Oct.12,
1990, now U.S. Pat. No. 5,082,909.
Claims
I claim:
1. A polymerization feed composition comprising: (a) a metathesis
polymerizable cycloolefin; (b) a metathesis polymerization catalyst
represented by the formula WOX.sub.4-x (OAr).sub.x ; wherein X is selected
from the group consisting of bromine, chlorine and fluorine; x is 1, 2 or
3 and OAr represents a mono-, di-, tri-, tetra-, or penta-substituted
phenoxy group, wherein the phenoxy group is substituted with substituents
selected from the group consisting of nitro, cyano, aldehyde, carboxy,
hydroxymethyl, alkoxy, alkylthio, arylthio, acyl, aroyl, acyloxy,
alkxoycarbonyl, cycloalkane, dialkylamino, diarylamino, alkyl sulfonyl,
aryl sulfonyl, alkyl sulfonate, aryl sulfonate, aryl, aralkyl, aryloxy,
and allyl groups; and (c) a catalyst activator.
2. The polymerization feed composition of claim 1 wherein X is chlorine.
3. The polymerization feed composition of claim 1 wherein said catalyst
activator is selected from the group consisting of trialklyaluminum,
dialkylaluminum halides, alkylaluminum dihalides, dialkyl(alkoxy)aluminum,
alkyl(alkoxy)aluminum halide; dialkylzincs, alkylzinc halides, diarylzinc,
arylzinc halides, alkylsilanes, tetraalkyltins, trialkyltin hydrides,
dialkyltin dihydrides, triaryltin hydrides, alkyllead hydrides and
aryllead hydrides.
4. The polymerization feed composition of claim 3 wherein said catalyst
activator is selected from the group consisting of ethylaluminum
dichloride, diethylaluminum chloride, triethylaluminum, diethylzinc,
dibutylzinc, ethyl-n-propoxyaluminum chloride, diphenylzinc,
tri-n-butyltin hydride, trioctyltin hydride, diphenyltin dihydride, and
triphenyltin hydride.
5. The polymerization feed composition of claim 1 wherein said cycloolefin
is a monomer selected from the group consisting of dicyclopentadiene,
higher order cyclopentadiene oligomers, norbornene, norbornadiene,
4-alkylidene norbornenes, dimethanohexahydronaphthalene,
dimethanohexahydronaphthalene, 5-vinyl-2-norbornene,
5-ethylidene-2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene,
ethylidenetetracyclododecane, methyltetracyclododecane, 5,6 dimethyl 2
norbornene, 5-ethyl 2-norbornene, 5-butyl-2-norbornene,
5-hexyl-2-norbornene, 5-octylnorbornene, 5-dodecyl-2-norbornene,
tetracyclododecane, hexacycloheptadecene, methyltetracyclododecene,
ethylidenetetracyclododecene and mixtures of two or more of said monomers.
6. The polymerization feed composition of claim 5 wherein said cycloolefin
is dicyclopentadiene.
7. The polymerization feed composition of claim 1 wherein said phenoxy
group is substituted with substituents selected from the group consisting
of cyclohexyl, phenyl, ethoxy, methoxy, cyclopropane, methyl sulfonyl, and
benzyl groups.
8. The polymerization feed composition of claim 1 further comprising a rate
moderator compound.
9. The polymerization feed composition of claim 8 wherein said rate
moderator compound is selected from the group consisting of phosphines,
phosphites, phosphinites, phosphonites, pyridines, and pyrazines.
10. The polymerization feed composition of claim 1 wherein said metathesis
polymerization catalyst further comprises a stabilizer compound.
11. The polymerization feed composition of claim 10 wherein said stabilizer
compound is a Lewis base.
12. The polymerization feed composition of claim 10 wherein said stabilizer
compound is selected from the group consisting of diethyl ether; ethylene
glycol dimethyl ether, 2-methoxyethyl ether, triethylene glycol dimethyl
ether, tetraethylene glycol dimethyl ether, benzonitrile, acetonitrile,
tetrahydrofuran, phenols having one aromatic ring, bisphenols having two
aromatic rings, polyphenols having more than two aromatic rings and
mixtures thereof.
13. The polymerization feed composition of claim 12 wherein said stabilizer
compound further comprises a phenol.
14. The polymerization feed composition of claim 12 wherein the stabilizer
compound is 2-methoxyethyl ether.
15. A polymerization feed composition comprising: (a) a metathesis
polymerizable cycloolefin; (b) a metathesis polymerization catalyst
represented by the formula WOX.sub.4-x (OAr).sub.x ; wherein X is selected
from the group consisting of bromine, chlorine and fluorine; X is 1, 2 or
3 and OAr represents a di-, tri-, tetra-, or penta-substituted phenoxy
group, wherein the phenoxy group is substituted with at lest one halogen
atom and at least one octyl or nonyl group, and (c) a catalyst activator.
16. The polymerization feed composition of claim 15 which additionally
comprises a stabilizer compound.
17. The polymerization feed composition of claim 16 wherein the stabilizer
compound is 2-methoxyethyl ether.
18. A process for preparing molded objects comprising charging to a mold a
liquid reaction mass comprising a metathesis polymerizable cycloolefin, a
metathesis polymerization catalyst, and a catalyst activator, wherein said
catalyst is represented by the formula WOX.sub.4-x (OAr).sub.x wherein X
is selected from the group consisting of bromine, chlorine and fluorine; x
is 1, 2 or 3 and Ar is a phenyl ring having 1-5 substituents selected from
the group consisting of nitro, cyano, aldehyde, carboxy, hydroxymethyl,
alkoxy, alkylthio, arylthio, acyl, aroyl, acyloxy, alkoxycarbonyl,
cycloalkane, dialkylamino, diarylamino, alkyl sulfonyl, aryl sulfonyl,
alkyl sulfonate, aryl sulfonate, aryl, aralkyl, aryloxy, and allyl groups,
and wherein after said liquid reaction mass is charged to said mold, said
reaction mass polymerizes in said mold.
19. The process of claim 18 wherein X is chlorine.
20. The process of claim 18 wherein said catalyst activator is selected
from the group consisting of trialkylaluminum, dialkylaluminum halides,
alkylaluminum dihalides, dialkyl(alkoxy)aluminum, alkyl(alkoxy)aluminum
halide; dialkylzincs, alkylzinc halides, diarylzinc, arylzinc halides,
alkylsilanes, tetraalkyltins, trialkyltin hydrides, dialkyltin dihydrides,
triaryltin hydrides, alkyllead hydrides and aryllead hydrides.
21. The process of claim 20 wherein said catalyst activator is selected
from the group consisting of alkylaluminum dichloride, diethylaluminum
chloride, triethylaluminum, diethylzinc, dibutylzinc, ethyl-n
propoxyaluminum chloride, diphenylzinc, tri-n-butyltin hydride,
trioctyltin hydride, diphenyltin dihydride, and triphenyltin hydride.
22. The process of claim 21 wherein said catalyst activator is
tri-n-butyltin hydride.
23. The process of claim 18 wherein said cycloolefin is a selected from the
group consisting of dicyclopentadiene, higher order cyclopentadiene
oligomers, norbornene, norbornadiene, 4-alkylidene norbornenes,
dimethanohexahydronaphthalene, dimethanohexahydronaphthalene,
5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methyl-2-norbornene,
5-phenyl-2-norbornene, ethylidenetetracyclododecane,
methyltetracyclododecane, 5,6-dimethyl 2-norbornene, 5-ethyl-2-norbornene,
5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octylnorbornene, 5 dodecyl-2
norbornene, tetracyclododecane, hexacycloheptadecene,
methyltetracyclododecene, ethylidenetetracyclododecene and mixtures of two
or more of said monomers.
24. The process of claim 23 wherein said cycloolefin is dicyclopentadiene.
25. The process of claim 18 wherein said phenyl ring is substituted with
substituents selected from the group consisting of cyclohexyl, phenyl,
ethoxy, methoxy, cyclopropane, methyl sulfonyl, and benzyl groups.
26. The process of claim 18 wherein said liquid reaction mass further
comprises a rate moderator compound.
27. The process of claim 26 wherein said rate moderator compound is
selected from the group consisting of phosphines, phosphites,
phosphinites, phosphonites, pyridines, and pyrazines.
28. The process of claim 18 wherein said metathesis polymerization catalyst
further comprises a stabilizer compound.
29. The process of claim 28 wherein said stabilizer compound is a Lewis
base.
30. The process of claim 28 wherein said stabilizer compound is selected
from the group consisting of diethyl ether; ethylene glycol dimethyl
ether, 2-methoxyethyl ether, triethylene glycol dimethyl ether,
tetraethylene glycol dimethyl ether, benzonitrile, acetonitrile,
tetrahydrofuran, phenols having one aromatic ring, bisphenols having two
aromatic rings, polyphenols having two aromatic rings, polyphenols having
more than two aromatic rings, and mixtures thereof.
31. The process of claim 30 wherein the stabilizer compound is
2-methoxyethyl ether.
32. The process of claim 29 wherein said stabilizer compound further
comprises a phenol.
33. A process for preparing molded objects comprising charging to a mold a
liquid reaction mass comprising a metathesis polymerizable cycloolefin, a
metathesis polymerization catalyst, and a catalyst activator, wherein the
catalyst is represented by the formula WOX.sub.4-x (OAr).sub.x wherein X
is selected from the group consisting of bromine, chlorine and fluorine; x
is 1, 2 or 3 and Ar is a phenyl ring having 2-5 substituents, wherein the
substituents on the phenyl ring are at least one halogen atom and at least
one octyl or nonyl group, and wherein after said liquid reaction mass is
charged to said mold, said reaction mass polymerizes in said mold.
34. The process of claim 33 wherein said metathesis polymerization catalyst
further comprises a stabilizer compound.
35. The process of claim 34 wherein the stabilizer compound is
2-methoxyethyl ether.
Description
FIELD OF THE INVENTION
This invention is a process for the bulk polymerization of metathesis
polymerizable cycloolefins, especially dicyclopentadiene, the polymer
prepared by this process and the catalyst system used in the process.
BACKGROUND OF THE INVENTION
Preparation of thermoset cycloolefin polymers via metathesis catalysts is a
relatively recent development in the polymer art. Klosiewicz, in U.S. Pat.
Nos. 4,400,340 and 4,520,181, teaches preparation of such polymers from
dicyclopentadiene and other similar cycloolefins via a two stream reaction
injection molding technique wherein a first stream, including the
catalyst, and a second stream, including a catalyst activator, are
combined in a mix head and immediately injected into a mold where, within
a matter of seconds, polymerization and molding to a permanently fixed
shape take place simultaneously.
In the typical system, according to Klosiewicz, the catalyst component is a
tungsten or molybdenum halide and the activator is an alkyl aluminum
compound. Most strained ring non conjugated polycyclic cycloolefins are
metathesis polymerizable. These include, for example, dicyclopentadiene,
higher order cyclopentadiene oligomers, norbornene, norbornadiene,
4-alkylidene norbornenes, dimethanooctahydronaphthalene,
dimethanohexahydronaphthalene and substituted derivatives of these
compounds, such as 5 vinyl-2-norbornene, 5-ethylidene-2-norbornene,
5-methyl 2-norbornene, 5-phenyl-2-norbornene,
ethylidenetetracyclododecane, methyltetracyclododecane,
5,6-dimethyl-2-norbornene, 5-ethyl 2-norbornene,
5-butyl-2-5-hexyl-2-norbornene, 5-octylnorbornene, 5-dodecyl-2-norbornene,
tetracyclododecane, hexacycloheptadecene, methyltetracyclododecene and
ethylidenetetracyclododecene. The preferred cycloolefin monomer is
dicyclopentadiene or a mixture of dicyclopentadiene with other strained
ring hydrocarbons in ratios of 1 to 99 mole % of either monomer,
preferably about 75 to 99 mole % dicyclopentadiene.
The metathesis catalyst system is comprised of two parts, i.e., a catalyst
component and an activator. The preferred catalyst component as taught by
Klosiewicz has been a tungsten halide, and preferably a mixture or complex
of tungsten hexachloride (WCl.sub.6) and tungsten oxytetrachloride
(WOCl.sub.4).
The tungsten or molybdenum compound of Klosiewicz is not normally soluble
in the cycloolefin, but can be solubilized by complexing it with a
phenolic compound.
In U.S. Pat. No. 4,981,931, by Bell, was disclosed tungsten catalyst
compositions for metathesis polymerization comprising
##STR1##
where X is Cl or Br, n is 2 or 3, R.sup.1 is a H, a Cl, an alkyl group
having 1-10 carbons, an alkoxy group having 1 to 8 carbons, or a phenyl
group, R.sup.2 is H or an alkyl group having 1 to 9 carbon atoms and
R.sup.3 is a H or an alkyl group having 1 to 10 carbon atoms for use with
a trialkyltin hydride or a triphenyltin hydride activator. A process to
employ such tin activator compounds in a system in which gelation and
polymerization were delayed for at least a time sufficient to charge the
reaction mixture to a mold. Both the catalyst and activator compounds had
improved stability, with resistance to oxygen and moisture. The catalyst
compounds were easy to isolate, instead of being mixtures as are those
found in the prior art. Although certain advantages were found, these
compounds when used to polymerize strained ring cycloolefins produced
polymers with a higher than desired residual monomer level.
It is therefore an object of this invention to provide a catalyst
composition that polymerizes strained ring polycyclic cycloolefins that
have very low levels of residual monomer.
There is also a need for polymers of the type described by Klosiewicz to
have higher levels of heat resistance, while maintaining other properties,
such as impact and tensile strengths at levels similar to those found in
prior art strained ring cycloolefin polymers. Previously, improved heat
resistance was obtained through use of comonomers with the
dicyclopentadiene (DCPD) monomer. The improved heat resistance was
previously obtained at the cost of decreased impact resistance. Therefore
it is a further object of this invention to provide catalyst compositions
that polymerize strained ring polycyclic cycloolefins producing polymers
with a higher level of heat resistance than prior art polymers while
maintaining their impact strength.
Another object of this invention is to find catalysts that are more
efficient in polymerizing dicyclopentadiene.
This invention is a process for preparing a polymer which comprises
contacting a strained ring polycyclic polyolefin with a substantially pure
tungsten complex, having the formula WOX.sub.4-x (OAr).sub.x wherein X
represents a halogen selected from the group consisting of bromine,
chlorine and fluorine; OAr represents a mono, di-, tri , tetra- or penta
substituted phenoxy group and where x is 1, 2 or 3. In the preferred
embodiments of this invention, X is chlorine. These catalysts are
efficient and promote catalysis of dicyclopentadiene at catalyst
concentration levels of 1 part catalyst to 4000 parts monomer or less.
Various activator compounds may be employed as are known in the art to act
together with the tungsten catalyst complexes described above to cause the
polymerization of strained ring polycyclic cycloolefins. Among the
activator compounds that can be employed in the practice of this invention
are trialkyltin hydrides, triaryltin hydrides, alkylaluminum compounds,
alkylalkoxyaluminum halides, diethylaluminum chloride, diethylzinc,
dibutylzinc, and triethylsilane. Mixtures of two or more activator
compounds may produce more desirable polymerization conditions and more
desirable polymer properties than a single activator compound in certain
situations.
Of the trialkyltin hydrides, suitable for use in the process of the
invention, tri-n-butyltin hydride is preferred. Among the triaryltin
hydrides is triphenyltin hydride.
As stated already hereinbefore the DCPD monomer used herein was of highly
pure grade, containing less than 2% impurities. The DCPD used in the
following examples was about 98-99% pure monomer. Other monomers or
comonomers employed in the practice of this invention should also be of
about this degree of purity. However, it is also contemplated that the
polymerization feed compositions of this invention can polymerize less
pure grades of dicyclopentadiene when the appropriate tungsten catalyst
compound, activator compound and other components are employed.
When the two parts of the catalyst system, the tungsten catalyst and the
tin activator, are combined, the resulting cycloolefin (for example, DCPD)
to catalyst compound ratio will be from about 500:1 to about 15,000:1 on a
molar basis, preferably 2000:1 and the molar ratio of the tungsten complex
versus the tin activator compound will be from about 1:2 to 1:6.
Generally the polymerization takes place in bulk, but the catalyst
components may be dissolved in a small amount of solvent, such as toluene.
It is preferred, however, to use DCPD as a solvent. When the liquid
tri-n-butyltin hydride activator compound is used, no solvent is necessary
for its addition and triphenyltin hydride is readily soluble in DCPD.
A preferred method in the practice of this invention for the polymerization
of DCPD is to contact a tungsten compound catalyst containing component
stream with a tin compound activator containing component stream wherein
at least one of the streams contains the DCPD. For example, it is possible
to dissolve the tungsten catalyst in DCPD and either to dissolve the
activator in DCPD or in another solvent or to use the activator without
any solvent. Usually both the tungsten catalyst and the tin activator are
first dissolved in separate streams of DCPD prior to the mixture of said
streams.
After the streams have contacted with each other the resulting mixture may
be injected or poured into a mold, where the polymerization takes place.
The polymerization is exothermic, but heating the mold from about 50 to
100.degree. C. is preferred.
The WOX.sub.4-x (OAr).sub.x complexes do not require any added solvent in
order that they may become soluble in DCPD solution. In general, the
solutions are quite stable in DCPD. The solutions can be used immediately,
or within 48 hours, in the polymerization of DCPD with a suitable
activator. When the tungsten complexes are stored in
dicyclopentadiene/2-methoxy ethyl ether (diglyme) solution (storage up to
four weeks at 40.degree. C.) the viscosity of the component remained
constant. No difference in reactivity has been observed for solutions with
added diglyme compared with those which possess no such additive. The
stability of the solutions can also be improved to eight weeks, and
beyond, by addition of an antioxidant, such as
2,6-di-tert-butyl-4-methylphenol. Monitoring of the tungsten phenoxide
species in solution by electrochemical measurements, e.g., cyclic
voltammetry, demonstrated that the integrity of the tungsten component is
maintained during storage.
During the polymerization of DCPD various additives can be included in the
reaction mixture to modify the properties of the polymer product of the
invention. Possible additives include fillers, pigments, antioxidants,
light stabilizers, plasticizers and polymeric modifiers.
The invention further relates to a two component catalyst system in which
the first component is a tungsten compound of the formula WOX.sub.4-x
(OAr).sub.x, wherein x is 1, 2 or 3; X is F, Cl or Br and wherein Ar
represents a phenyl ring substituted with one or more of the following
substituents: hydrogen (H), bromo (Br), chloro (Cl), fluoro (F), iodo (I),
nitro (NO.sub.2), cyano (CN), aldehyde (CHO), carboxy (COOH),
hydroxymethyl (CH.sub.2 OH), alkoxy (OR), alkylthio (SR), arylthio (SAr),
acyl (COR), aroyl (COAr), acyloxy (OCOR), alkoxycarbonyl (COOR),
cycloalkanes (cyclo R), dialkylamino (NR.sub.2), diarylamino (NAr.sub.2),
alkylsulfonyl (SO,R), arylsulfonyl (SO.sub.2 Ar), alkylsulfonate (SO.sub.2
OR), arylsulfonate (SO.sub.2 OAr), aryl (Ar), aralkyl (CH.sub.2 Ar),
aryloxy (OAr), aIkyI groups containing 1-20 carbon atoms, fluoroalkyl
groups containing 1 to 10 carbon atoms and allyl (--CH.sub.2
--CH.dbd.CH.sub.2). Among the most preferred molecules or groups that are
substituted on the phenyl ring include methyl, ethyl, isopropyl,
tert-butyl, cyclohexyl, octyl, nonyl, phenyl, bromo, chloro, fluoro,
ethoxy (OEt), methoxy (OMe), cyclopropane (cyclo-C.sub.3 H.sub.5),
trifluoromethyl, methylsulfonyl (SO.sub.2 Me), and benzyl (CH.sub.2
C.sub.6 H.sub.5). The substituents need not be identical on a particular
phenyl ring. For example, a trisubstituted phenyl group such as
2,4-dichloro-6-methyl phenyl. A generalized formula to take the case of
the mixed substituents into consideration is, e.g., WOCl.sub.p (OAr).sub.q
(OAr).sub.r where p + q + r = 4. Mono, di, tetra, and penta substituted
phenols, as well as the aforementioned tri substituted phenols, can also
be employed in making the tungsten compounds employed in this invention.
The desired tungsten compounds are prepared by reacting the appropriate
phenol with WOCl.sub.4 in solution. The molar ratio of phenol to
WOCl.sub.4 is about equal to x in the generalized formula WOCl.sub.4-x
(OAr).sub.x. The invention is also contemplated to include the use of
mixtures of two or more different tungsten compounds. The phenyl ring,
symbolized by Ar in the above general formula, may have R substituted at
the 1, 2, 3, 4 or 5 positions. In the monosubstituted phenyl ring, R may
be at the 2, 3 or 4 positions. In the disubstituted phenyl ring the
substituents R.sub.1 and R may be at the 2,6; 2,5; 2,4; 2,3; 3,4; or 3,5
positions. R and R.sub.1 may be the same or different groups. In the
trisubstituted phenyl ring substituents R, R.sub.1 and R.sub.2 may be at
the 2,3,4; 2,3,5; 2,3,6; 2,4,5; 2,4,6 or the 3,4,5 positions, where R,
R.sub.1 and R.sub.2 may be the same or different. The tetra substituted
structures for the phenyl ring have substituents at the 2,3,4,6; 2,3,5,6
or the 2,3,4,5 positions, where R, R.sub.1, R.sub.2, and R.sub.3 may be
the same or different. An example of such would be made from 2,3,5,6
tetrachlorophenol. The penta substituted ring has substituents at the
2,3,4,5 and 6 positions, where each substituent may be the same or
different. An example of the penta substituted structure would be made
from C.sub.6 F.sub.5 OH.
The second component of the catalyst system is an activator compound that
in combination with the tungsten compound is capable of yielding a
catalyst able to polymerize DCPD in bulk. Such activators or co catalysts
include, for example organoaluminum compounds such as trialklyaluminum,
dialkylaluminum halides, alkylaluminum dihalides, dialkyl(alkoxy)aluminum,
alkyl(alkoxy)aluminum halide; dialkylzincs, alkylzinc halides, diarylzinc,
arylzinc halides, alkylsilanes (RSiH.sub.3, R.sub.2 SiH.sub.2 and R.sub.3
SiH, where R is an alkyl group), tetraalkyltins, trialkyltin hydrides,
dialkyltin dihydrides, triaryltin hydrides and the corresponding alkyl and
aryl lead hydrides. Specific examples of activators include ethylaluminum
dichloride, diethylaluminum chloride, triethylaluminum, diethylzinc,
dibutylzinc, ethyl n propoxyaluminum chloride, diphenylzinc, tributyltin
hydride, trioctyltin hydride, diphenyltin dihydride, and triphenyltin
hydride. Preferred activators include triphenyltin hydride and trialkyltin
hydrides, such as a tributyltin hydride.
In order to maintain the stability of tungsten compounds of the present
invention with the 98-99% dicyclopentadiene without premature gelation, it
is usually necessary to add a stabilizer compound to the solution
containing the tungsten compound, and a rate moderator to the solution
containing the tin activator compound. It is preferred to store the
tungsten compounds in solution in dicyclopentadiene. When the stabilizer
compound is omitted, a slow polymerization of the monomer proceeds in the
storage container. Stabilizer compounds include diethyl ether (OEt.sub.2);
ethylene glycal dimethyl ether (monoglyme), Z-Methoxyethyl ether
(diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene
glycol dimethyl ether (tetraglyme), benzonitrile, acetonitrile,
tetrahydrofuran, phenols with one aromatic ring {such as
2,6-di-t-butyl-4-methylphenol (BHT) or
2,6-di-tert-butyl-4-sec-butylphenol, e.g., Isonox 132}, bisphenols with
two aromatic rings {such as 4,4'-methylenebis(2,6-dimethylphenol) sold
under the tradename Lowinox 44M26 by Lowi Chemical Company of Akron, Ohio;
4,4'-methylenebis(2,6-di-tert-butylphenol sold under the tradename Lowinox
002; 2,2'-methylenebis(4-ethyl-6-butylphenol) sold under the tradename
Cyanox 425; 2,2'-ethylenebis(4,6-di-tert-butylphenol sold under the
tradename Vanox 1290;
2,2'-methylenebis-(4-ethyl-6-(1-methylcyclohexyl)phenol sold under the
tradename Permanax WSP; 4,4'-butylidenebis(6-tert-butyl-3-methylphenol)
sold under the tradename Lowinox 44B25; 4,4'-thiobis(6-tert
butyl-3-methylphenol sold under the tradename Lowinox 44S36;
1,1'-thiobis-(2-naphthol) sold under the tradename SAO 30;
2,2'-thiobis(4-methyl-6-tert-butylphenol) sold under the tradename SAO-6;
2,2'-isobutylidene-bis(4,6-dimethylphenol sold under the tradename Lowinox
22IB46; or 2,2'-methylenebis(4-methyl-6-cyclohexyl)phenol) sold under the
tradename Vulkanox ZKF} or polyphenols with more than two aromatic rings
{such as
1,3,5-trimethyl-2,4-6-tris(3,5-di-t-butyl-4-hydroxybenzene)benzene sold
under the tradename Ethyl Antioxidant 330; sterically hindered polynuclear
phenols sold under the tradename Lowinox 22CP46 and Lowinox CPL by Lowi
Chemical Company or the butylated reaction product of p-cresol and
dicylopentadiene such as Wingstay L powder sold by the Goodyear Tire and
Rubber Company of Akron, Ohio} may also be used. In addition, mixtures of
the above stabilizer compounds such as a mixture of diglyme and one or
more phenols or other Lewis bases can be employed in the practice of this
invention.
The rate moderator compound prevents the polymerization process from being
too rapid, provides for adequate mixing of the catalyst components, and
allows the mold to be completely filled. The rate moderator compounds
include various nitrogen or phosphorus compounds used for this purpose as
described in U.S. Pat. Nos. 4,727,125; 4,883,849; and 4,933,402. These
rate moderators are generally selected from the group consisting of
phosphines, phosphites, phosphinites, phosphonites, pyridines, and
pyrazines. Preferred rate moderators include pyridine (py); pyrazine
(pyz); 2,6-dimethylpyrazine (Me.sub.2 pyz); tributylphosphine (Bu.sub.3
P); triethylphosphine (PEt.sub.3); tricyclohexylphosphine (PCy.sub.3);
triphenylphosphine (PPh.sub.3); methyldiphenylphosphine (PMePh.sub.2);
dimethylphenylphosphine (PMe.sub.2 Ph); triethylphosphite (P(Oet).sub.3);
tributylphosphite (P(OBu).sub.3); triisopropylphosphite (P(O-i-Pr).sub.3);
ethyldiphenylphosphonite (P(OEt)Ph.sub.2 ; triphenylphosphite
(P(OPh).sub.3); triisopropylphosphine (P-i-Pr.sub.3); trimethylphosphite
(P(OMe).sub.3); tri-tert butylphosphine (P tert-Bu.sub.3);
diethylphenylphosphonite (P(OEt).sub.2 Ph); and tribenzylphosphine
(P(CH.sub.2 Ph).sub.3). The more preferred rate moderators are phosphines
and phosphites, e.g., tributylphosphine (Bu.sub.3 P) and tributylphosphite
((BuO).sub.3 P). The stabilizer and rate moderator compounds are not
necessary when lower purity dicyclopentadiene is employed, unless
prolonged storage times are desired. Also, the stabilizer is not necessary
when prolonged storage of the catalyst in the monomer is not desired.
In some embodiments of this invention, a preformed elastomer which is
soluble in the reactant streams is added to the metathesis catalyst system
in order to increase the impact strength of the polymer. The elastomer is
dissolved in either or both of the reactant streams in an amount from
about 3 to about weight percent range, based on the weight of monomer.
Illustrative elastomers include natural rubber, butyl rubber,
polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene
copolymer, styrene butadiene-styrene triblock rubber, random styrene
butadiene rubber, styrene-isoprene-styrene triblock rubber,
ethylene-propylene-diene terpolymers, ethylene vinyl acetate, and nitrile
rubbers. Various polar elastomers can also be emp The amount of elastomer
used is determined by its molecular weight and is limited by the viscosity
of the resultant reactant streams. The resultant reactant streams
containing elastomer cannot be so viscous that mixing is not possible.
Although the elastomer can be dissolved in either one or both of the
streams, it is desirable that it be dissolved in both.
In addition to measuring gel and cure times and residual DCPD monomer
level, a measurement of swell value was made. The swell value is an
indication of the degree of crosslinking in the polymer, i.e., lower swell
values indicate higher degree of crosslinking. The general procedure used
for swell value determinations is as follows: A 5 gram sample of polymer
is removed from its test tube (by breaking the glass) and carefully sliced
into 1-2 mm thick sections across the cylindrical axis with a tile cutter.
The burrs are removed, each slice weighed to the nearest milligram and
strung onto a stainless steel or copper wire taking care to keep them in
known sequence. This is done for each sample at a given monomer feed. The
wire is made into a closed loop and placed in 50 ml of toluene for each
gram of polymer. These flasks are then heated to reflux for 16 hours
(overnight) and cooled. Each loop is successively removed from the flask
and placed in a small dish of fresh toluene. The slices are removed,
patted dry, and weighed individually, again taking care not to disturb
their sequence or to tear the swollen samples. The swell values are
calculated using the following formula: swell (%)= (w.sub.2
-w.sub.1)/w.sub.1 .times.100%, where w.sub.1 = initial weight of polyDCPD
sample and w.sub.2 = weight of solvent swollen polyDCPD sample. Since the
swell value is an indication of the degree of crosslinking in the polymer,
low values are preferred.
The best mode now contemplated of carrying out this invention will be
illustrated with the following examples. The examples are given for the
purpose of illustration only and the invention is not to be regarded as
limited to any of the specific materials or conditions used in the
examples.
In the following examples, in which tungsten complex catalyst components
are prepared, tungsten hexachloride (WCl.sub.6) was obtained from GTE
Sylvania Chemical Company and used as received. 2,6-diisopropylphenol and
2,6-dichloro-phenol (HOC.sub.6 H.sub.3 -2,6-Cl.sub.2) were purchased from
Aldrich Chemical Company and used as received. Hexamethyldisiloxane
(Me.sub.3 SiOSiMe.sub.3) (Aldrich) was sparged with dry nitrogen before
use.
Cyclopentane, diethyl ether, and pentane were dried over 4A molecular
sieves and sparged with nitrogen prior to use. Toluene was placed in
contact with 13X molecular sieves and sparged with dry nitrogen before
use.
All operations were carried out under a dry nitrogen atmosphere or in
vacuum either in a Vacuum Atmospheres Dri Lab (inerted by argon gas) or
using Schlenk techniques. All solvent transfers were performed by cannula
or syringe techniques to maintain an inert atmosphere.
In the Examples in which polymerization studies are set forth, the
following general procedures were followed. All manipulations were
performed anaerobically in nitrogen-sparged pop bottles or under an argon
atmosphere (Vacuum Atmospheres Dri Lab) or using Schlenk techniques.
Tri-n-butyltin hydride (packaged in Sure/Seal bottle) was purchased from
Aldrich Chemical Company and stored refrigerated (0.degree. C.). Diglyme
was dried by placing it over 3A molecular sieves and sparged with nitrogen
before use. Where necessary rate moderators, such as tributylphosphite
(Albright and Wilson), were dried over molecular sieves and sparged with
dry nitrogen prior to use.
Polymerizations were conducted in nitrogen-sparged test tubes by adding
together the catalyst and activator components (2.5 ml of each), mixing on
a vortex mixer and then inserting the tube into an oil bath at 80.degree.
C. or higher or into a heated block at about 33.degree. C. Gel times were
estimated by observing the initial viscosity change and the times were
taken when the polymerization increased the exotherm to 100.degree. C.
(T.sub.100.degree. C.) or 180.degree. C. (T.sub.180.degree. C.), and to
the maximum temperature of the polymerization (T.sub.max). Polymer swells
were obtained by refluxing the samples in toluene for 16 hours, cooling
for four hours and determining the percentage weight gain.
The tungsten starting material used in all catalyst preparation is tungsten
oxytetrachloride complex (WOCl.sub.4). This compound was prepared in the
following manner. A solution of hexamethyl-disiloxane (HMDS) (13.40 ml,
0.063 mol) in toluene (100 ml) was added dropwise into a toluene (200 ml)
solution of WCl.sub.6 (25 g; 0.063 mol) in a 500 ml round bottomed flask
(with stirring) over a 75 minute period. After the HMDS addition was
completed, the column was removed and the reaction mixture was allowed to
stir overnight under nitrogen. The brown solution was filtered in the dry
box to yield a quantity of crude, orange WOCl.sub.4 (19.02 g; 88% yield).
Immediately before use, the crude material was sublimed under reduced
pressure at 100.degree. C. in small portions to give bright orange
crystalline WOCl.sub.4. Pure commercial quantities of WOCl.sub.4 may be
substituted in any of the catalyst preparations.
EXAMPLE 1
A tungsten phenoxide catalyst having the formula WOCl.sub.2 (OC.sub.6
H.sub.3 -2,6-i-Pr.sub.2).sub.2 was prepared in the following manner. The
addition of two moles of the phenol for each mole of WOCl.sub.4 produced
the desired tungsten phenoxide compound. A quantity of WOCl.sub.4 (5 g;
0.0146 moles) was placed in a pop bottle together with a stir bar. Toluene
(50 mL) was added to the WOCl.sub.4 by cannula followed by the dropwise
addition of neat 2,6-diisopropylphenol (HOC.sub.6 H.sub.3 -2,6-i-Pr.sub.2)
(5.42 mL; 0.0296 mo1). The reaction mixture was allowed to stir at room
temperature for three days under a nitrogen sparge. After this time, the
reaction mixture was taken into the dry box, scraped from the bottle, and
further dried under reduced pressure. The complex WOCl.sub.2 (OC.sub.6
H.sub.3 -2,6-i-Pr.sub.2).sub.2 (8.83 g; 97% yield) was obtained as a dark
purple solid.
Alternatively the catalyst may be prepared in accordance with the following
procedure: To a quantity of WOCl.sub.4 (5 g; 0.0146 moles) stirring in
cyclopentane (100 Ml) was added dropwise a solution of
2,6-diisopropylphenol (HOC.sub.6 H.sub.3 -2,6-i-Pr.sub.2) (5.42 mL; 0.0296
mol) in cyclopentane (50 mL). The dropwise addition of the phenolic
solution was accomplished over a period of 30 minutes and accompanied by
the solution changing from orange to deep red. The reaction was allowed to
stir at room temperature for two hours. After this time, the reaction
mixture was taken into the dry box and filtered. No solids were collected
and the filtrate was evaporated to dryness under reduced pressure. The
complex WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2 (8.22 g; 90%
yield) was obtained as a crystalline dark purple solid.
EXAMPLE 2
A tungsten phenoxide catalyst having the formula WOCl.sub.3 (OC.sub.6
H.sub.3 -2,6-Cl.sub.2) was made by mixing WOCl.sub.4 (3.79 g; 0.0111
moles) in cyclopentane (50 ml). A dropwise solution of 2,6-dichlorophenol
(1.18 ml; 0.111 mole) in cyclopentane (25 ml) was then added dropwise over
a period of 30 minutes. During the phenol addition the solution changed
color from orange to deep red and purple crystals precipitated from the
reaction solution. The reaction was allowed to stir at room temperature
for two hours. After this time the reaction mixture was taken into the dry
box and filtered. The solids collected by filtration were washed with 10
ml of pentane and dried in vacuum, yielding 4.20 g (81%). The filtrate was
evaporated to dryness under reduced pressure and was determined to be the
same complex as the solid. The complex obtained, WOCl.sub.3 (OC.sub.6
H.sub.3 -2,6-Cl.sub.2) was obtained as a dark red purple solid. Other
WOCl.sub.3 (OAr) compounds can be prepared by substitution of other
phenols for 2,6-dichlorophenol.
EXAMPLE 3
A quantity (3.5 g; 7.475 mmol) of the product of Example 2 was used to make
a tungsten phenoxide compound having the formula WOCl.sub.2 (OC.sub.6
H.sub.3 -2,6-Cl.sub.2).sub.2. Said quantity was dissolved in a minimum
quantity of diethyl ether (50 ml). A saturated solution of lithium
2,6-dichlorophenoxide (LiOC.sub.6 H.sub.3 -2,6-Cl.sub.2) (1.28 g ml; 7.58
mmol) in diethyl ether (about 8 ml) was slowly added dropwise. Almost
instantly, the deposition of red crystals occurred. The reaction mixture
was stirred at room temperature with a slow nitrogen purge over the ether
solution for 150 minutes. After an additional one hour of stirring, the
reaction mixture was filtered to remove a dark red crystalline WOCl.sub.3
(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2. The solid was then washed with a
small volume of dried pentane (5 ml) and the solid dried under vacuum
(3.90 g). This material was dissolved in dichloromethane (about 25 ml) and
filtered to remove the lithium chloride by product. Evaporation of the
filtrate under reduced pressure led to pure product in 72% yield (3.21 g).
EXAMPLE 4
In Example 4, stock solutions of the catalyst mixtures were prepared by
charging a ten ounce pop bottle with the appropriate measure of WOCl.sub.3
(OC.sub.6 H.sub.3 -2,6-Cl.sub.2) prepared according to the process of
Example 2 (a shorthand for referring to the tungsten catalyst compound in
this example and in the following examples is "W"), DCPD and diglyme (DG).
The activator solution was prepared by mixing tri-n-butyltin hydride
(n-Bu.sub.3 SnH); the appropriate quantity of tributylphosphite (TBP) and
DCPD in a 10 ounce pop bottle. The following table indicates the amounts
of materials used in preparing these two solutions.
______________________________________
A-Component B-Component
DCPD:n-Bu.sub.3 SnH:TBP
DCPD:W:DG
______________________________________
2000:1:2:2:3
1000:2:3 1000:1:2
50:0.39:0.60 (mL)
50:0.172:0.11 (mL)
2000:1:2:3:3
1000:3:3 1000:1:2
50:0.59:0.60 (mL)
50:0.172:0.11 (mL)
______________________________________
The final reaction ratio for mixed catalyst and activator components varied
DCPD:W:diglyme:n-Bu.sub.3 SnH:TBP = 2000:1:2:2:3 to 2000:1:2:3:3 (see
Table 1)
TABLE 1
__________________________________________________________________________
DCPD Polymerization By WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2)/n-Bu.su
b.3 SnH Mixtures
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:Sn:TBP
(.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:2:3
30 1 8 13 26 206
78.8
0.09
2000:1:2:2:3
30 1 7 13 29 206
-- --
2000:1:2:2:3
80 1 8 13 26 210
85.0
0.25
2000:1:2:3:3
30 1 4 11 24 195
-- --
2000:1:2:3:3
30 1 4 10 22 203
79.2
0.12
2000:1:2:3:3
80 1 5 12 26 207
82.7
0.23
__________________________________________________________________________
EXAMPLE 5
In Example 5 the catalyst stock solution was prepared by charging a 10 oz
pop bottle with the appropriate amount of WOCl.sub.2 (OC.sub.6 H.sub.3
-2,6-Cl.sub.2).sub.2, DCPD and DG. Stock solutions of the activator were
prepared by charging a 10 oz pop bottle with the appropriate amounts of
n-Bu.sub.3 SnH and TBP. The following table indicates the amounts of
materials used.
__________________________________________________________________________
Reaction Ratio A-Component B-Component
DCPD:W:DG:n-Bu.sub.3 SnH:TBP
DCPD:n-Bu.sub.3 SnH:TBP
DCPD:W:DG
__________________________________________________________________________
1000:3:2 1000:1:2
2000:1:2:2:3 100 mL:0.39 mL:0.40 mL
100 mL:0.44 g.022 mL
2000:3:2 2000:1:2
4000:1:2:2:3 100 mL:0.20 mL:0.20 mL
100 mL:0.22 g:0.11 mL
4000:3:2 4000:1:2
8000:1:2:2:3 100 mL:0.10 mL:0.10 mL
100 mL:0.11 g:0.05 mL
1000:3:2 1000:1:2
2000:1:2:3:3 100 mL:0.59 mL:0.59 mL
100 mL:0.44 g:0.22 mL
2000:3:2 2000:1:2
4000:1:2:3:3 100 mL:0.30 mL:0.30 mL
100 mL:0.22 g.0.11 mL
4000:3:2 4000:1:2
8000:1:2:3:3 100 mL:0.15 mL:0.15 mL
100 mL:0.11 g:0.05 mL
__________________________________________________________________________
The final reaction ratio for mixed catalyst and activator components was
varied from DCPD:W:diglyme:n-Bu.sub.3 SnH:TBP = 2000:2:8:3 to 8000:1:2:8:3
(see Table 2).
TABLE 2
__________________________________________________________________________
DCPD Polymerization By WOCL.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2
/n-Bu.sub.3 SnH Mixtures
Effect of DCPD:WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2 Ratio On
Residual DCPD Levels
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:Sn:TBP
(.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:2:3
30 10 32 38 51 208
79.0
0.04
2000:1:2:2:3
80 8 17 22 34 208
90.5
0.09
4000:1:2:2:3
33 6 22 27 40 208
76.5
0.07
4000:1:2:2:3
80 8 16 22 36 211
85.7
0.21
8000:1:2:2:3
33 7 33 36 51 209
76.7
0.17
8000:1:2:2:3
80 6 21 28 39 192
91.3
0.57
2000:1:2:3:3
30 8 25 31 43 204
80.6
0.11
2000:1:2:3:3
80 8 17 21 32 212
94.9
0.16
4000:1:2:3:3
33 4 21 27 39 207
80.0
0.12
4000:1:2:3:3
80 4 16 22 37 215
91.6
0.22
8000:1:2:3:3
33 5 23 29 42 204
75.6
0.40
8000:1:2:3:3
80 5 19 24 38 209
90.0
0.44
__________________________________________________________________________
EXAMPLE 6
In Example 6 the catalyst stock solution was prepared by charging a 10 oz
pop bottle with the appropriate amount of WOCl.sub.2 (OC.sub.6 H.sub.3
-2,6-i-Pr.sub.2).sub.2, DCPD and diglyme. Stock solutions of the activator
were prepared by charging a 10 oz pop bottle with the appropriate amounts
of n-Bu.sub.3 SnH and tributylphosphite ((TBP). The following table
indicates the amounts of materials used.
__________________________________________________________________________
Reaction Ratio A-Component B-Component
DCPD:W:DG:n-Bu.sub.3 SnH:TBP
DCPD:n-Bu.sub.3 SnH:TBP
DCPD:W:DG
__________________________________________________________________________
1000:1:3 1000:1:2
2000:1:2:1:3 100 mL:0.20 mL:0.60 mL
100 mL:0.44 g:022.mL
1000:2:3 1000:1:2
2000:1:2:2:3 100 Ml:0.40 mL:0.60 mL
100 mL:0.44 g:0.22 mL
1000:3:2 1000:1:2
2000:1:2:3:3 100 mL:0.59 mL:0.60 mL
100 mL:0.44 g:0.22 mL
1000:6:3 1000:1:2
2000:1:2:6:3 100 mL:1.18 mL:0.60 mL
100 mL:0.44 g:0.22 mL
1000:8:3 1000:1:2
2000:1:2:8:3 100 mL:1.48 mL:0.60 mL
100 mL:0.44 g:0.22 mL
__________________________________________________________________________
The final reaction ratio for mixed catalyst and activator components was
varied from DCPD:W:diglyme:n-Bu.sub.3 SnH:TBP = 2000:1:2:1:3 to
2000:1:2:8:3 (see Table 3)
TABLE 3
__________________________________________________________________________
DCPD Polymerization By WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2
/n-Bu.sub.3 SnH Mixtures:
Effect of WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2 /n-Bu.sub.3
SnH Ratio On Residual DCPD Levels
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:Sn:TBP
(.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:1:3
33 15 50 55 70 210
88.1
0.12
2000:1:2:1:3
80 12 29 41 49 190
103.8
2.04
2000:1:2:2:3
33 8 30 34 46 208
90.8
0.06
2000:1:2:2:3
80 7 19 22 34 211
102.1
0.12
2000:1:2:3:3
30 8 25 31 43 204
80.6
0.11
2000:1:2:3:3
80 8 17 21 32 212
94.9
0.16
2000:1:2:6:3
33 1 13 17 30 200
94.9
0.30
2000:1:2:6:3
80 1 12 17 29 210
109.5
0.38
2000:1:2:8:3
34 1 10 16 29 211
97.6
0.54
2000:1:2:8:3
80 1 10 16 29 202
103.1
0.50
__________________________________________________________________________
EXAMPLE 7
In Example 7 the stock solution of the catalyst was prepared by mixing the
appropriate amounts of WOCl.sub.2 (OC.sub.6 H.sub.3
-2,6-i-Pr.sub.2).sub.2, DCPD and DG in a 10 oz pop bottle. Activator stock
solutions were prepared by charging a 10 oz pop bottle with the
appropriate amounts of n-Bu.sub.3 SnH and TBP. The following table
indicates the amounts of materials used. The final reaction ratio for
mixed catalyst and activator components was varied from
DCPD:W:diglyme:n-Bu.sub.3 SnH:TBP = 2000:1:2:3:0 to 2000:1:2:3:4 (see
Table 4)
EXAMPLE 8
In Example 8, various Lewis bases were used to delay polymerization with a
WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2 catalyst compound and
n-Bu.sub.3 SnH activator compound. Among the Lewis bases were
tributylphosphite ((BuO).sub.3 P), pyridine (py); 2,6-dimethylpyridine
(2,6-Me.sub.2 py); pyrazine (pyz), 2,6-dimethylpyrazine (2,6-Me.sub.2
pyz); triisopropylphosphite ((i-PrO).sub.3 P); dibutylphosphite
((BuO).sub.2 P(O)H) and tributylphosphine (Bu.sub.3 P). The same general
polymerization procedure was employed as was previously explained herein.
The proportions of dicyclopentadiene (DCPD): tungsten catalyst (W):
diglyme (DG): tri-n-butyltin hydride (Sn): Lewis base (LB) is shown in the
results that are shown in Table 5.
__________________________________________________________________________
Reaction Ratio A-Component B-Component
DCPD:W:DG:n-Bu.sub.3 SnH:TBP
DCPD:n-Bu.sub.3 SnH:TBP
DCPD:W:DG
__________________________________________________________________________
1000:3:2 1000:1:2
2000:1:2:3:2 100 mL:0.59 mL:40 mL
100 mL:0.50 g:021 mL
1000:3:3 1000:1:2
2000:1:2:3:3 100 mL:0.59 mL:0.59 mL
100 mL:0.50 g:0.21 mL
1000:3:4 1000:1:2
2000:1:2:3:4 100 mL:0.59 mL:0.79 mL
100 mL:0.50 g:0.21 mL
1000:3:8 1000:1:2
2000:1:2:3:8 100 mL:0.59 mL:1.59 mL
100 mL:0.50 g:0.21 mL
__________________________________________________________________________
TABLE 4
__________________________________________________________________________
DCPD Polymerization By WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2)/n-Bu.su
b.3 SnH Mixtures
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:Sn:TBP
(.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:3:2
33 5 16 21 33 207
91.4
0.10
2000:1:2:3:2
33 4 18 23 35 208
-- --
2000:1:2:3:2
80 5 14 18 30 210
102.9
0.15
2000:1:2:3:2
80 4 14 19 31 207
-- --
2000:1:2:3:3
30 8 25 31 43 204
80.6
0.11
2000:1:2:3:3
30 8 29 34 47 205
-- --
2000:1:2:3:3
80 8 17 21 32 212
94.9
0.16
2000:1:2:3:3
80 8 17 21 37 215
-- --
2000:1:2:3:4
33 9 31 37 49 207
96.0
0.15
2000:1:2:3:4
33 9 33 38 49 199
-- --
2000:1:2:3:4
80 8 18 23 36 212
111.1
0.27
2000:1:2:3:4
80 9 19 24 36 213
-- --
2000:1:2:3:4
33 16 63 66 80 206
96.7
0.17
2000:1:2:3:8
33 19 66 72 85 202
-- --
2000:1:2:3:8
80 13 25 31 45 217
106.8
0.26
2000:1:2:3:8
80 14 24 30 45 217
-- --
__________________________________________________________________________
TABLE 5
__________________________________________________________________________
Activation of WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2 By
n-Bu.sub.3 SnH: Effect of Various Lewis Bases
Lewis Initial Residual
Base Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:Sn:LB
(LB) (.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:3:3
(BuO).sub.3 P
30 7 23 28 41 206
75.9
0.35
2000:1:2:3:3
(BuO).sub.3 P
80 9 24 30 45 211
95.5
0.33
2000:1:2:3:3
py 31 90 319 -- 345 175
160.4
0.39
2000:1:2:3:3
py 80 40 53 57 78 212
145.2
0.63
2000:1:2:3:3
2,6-Me.sub.2 py
30 1 15 21 33 204
94.1
0.37
2000:1:2:3:3
pyz 30 14 331 -- 275 175
176.9
0.34
2000:1:2:3:3
pyz 80 10 49 52 65 211
162.2
0.77
2000:1:2:3:3
2,6-Me.sub.2 pyz
30 12 60 69 85 198
147.0
0.39
2000:1:2:3:3
2,6-Me.sub.2 pyz
80 10 32 37 48 208
143.0
0.49
2000:1:2:3:3
(i-PrO).sub. 3 P
30 14 25 30 47 210
71.8
0.29
2000:1:2:3:3
(i-PrO).sub.3 P
80 10 15 22 38 204
82.0
0.65
2000:1:2:3:3
(BuO).sub.2 P(O)H
31 44 86 91 108 205
91.9
0.31
2000:1:2:3:3
(BuO).sub.2 P(O)H
80 22 31 39 58 212
98.4
0.68
2000:1:2:3:3
iBu.sub.3 P
80 100
120 128 140 220
115.8
0.63
__________________________________________________________________________
EXAMPLE 9
In Example 9, the effect of various Lewis bases upon polymerization and the
polymer produced was conducted with WOCl.sub.2 (OC.sub.6 H.sub.3
-2,6-Cl.sub.2).sub.2 tungsten phenoxide catalysts and tri-n-butyltin
hydride activator. The abbreviations in the following Table 6 are the same
as explained in Example 8.
EXAMPLE 10
In Example 10 the effect of tributylphosphine upon polymerization when
using a WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2 (example 1)
catalyst was determined. The effect upon polymerization is seen in Table
7.
EXAMPLE 11
In Example 11 a similar comparison of the effect of tributylphosphine was
conducted as in Example 9 with WOCl.sub.2 (OC.sub.6 H.sub.3
-2,6-Cl.sub.2).sub.2 as the tungsten catalyst. The results are shown in
Table 8.
TABLE 6
__________________________________________________________________________
Activation of WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2 By
n-Bu.sub.3 SnH: Effect of Various Lewis Bases
Lewis Initial Residual
Base Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:Sn:TBP
(LB) (.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:3:3
(BuO).sub.3 P
30 7 25 31 47 207
82.1
0.12
2000:1:2:3:3
(BuO).sub.3 P
80 7 20 24 40 212
994.1
0.20
2000:1:2:3:3
py 30 120
254 268 282 198
91.7
0.35
2000:1:2:3:3
py 80 29 36 39 55 219
114.8
0.26
2000:1:2:3:3
pyz 30 1 33 42 58 195
98.9
0.37
2000:1:2:3:3
2,6-Me.sub.2 py
30 8 31 41 48 188
88.6
0.50
2000:1:2:3:3
2,6-Me.sub.2 pyz
80 5 16 24 35 200
94.1
0.43
2000:1:2:3:3
(i-PrO).sub.3 P
30 1 134 19 31 203
78.1
0.17
2000:1:2:3:3
(BuO).sub.2 P(O)H
30 66 202 212 230 200
87.3
0.13
2000:1:2:3:3
(BuO).sub.2 P(O)H
80 23 30 33 47 213
90.6
0.23
2000:1:2:3:3
Bu.sub.3 P
80 90 123 129 140 230
95.3
0.28
__________________________________________________________________________
TABLE 7
__________________________________________________________________________
Polymerization Using WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2
/n-Bu.sub.3 SnH: Effect of
Tributylphosphine (Bu.sub.3 P)
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:Sn:Bu.sub.3 P
(.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:3:1
80 56 73 76 90
223
-- --
2000:1:2:3:1
80 55 76 78 100
229
129.8
1.36
2000:1:2:3:2
80 76 98 102 118
224
145.5
0.66
2000:1:2:3:2
80 70 93 98 116
222
-- --
2000:1:2:3:3
80 100
120 128 248
220
115.8
0.63
2000:1:2:3:3
80 100
124 128 150
228
120.6
0.96
__________________________________________________________________________
TABLE 8
__________________________________________________________________________
Polymerization Using WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2
/n-Bu.sub.3 SnH: Effect of
Tributylphosphine (Bu.sub.3 P)
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:Sn:Bu.sub.3 P
(.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:3:1
32 81 160 163 177
205
83.9
0.17
2000:1:2:3:1
32 150
218 223 235
202
-- --
2000:1:2:3:1
80 24 30 46 60
215
-- --
2000:1:2:3:1
80 30 40 46 64
222
89.1
0.24
2000:1:2:3:2
80 74 84 87 112
227
-- --
2000:1:2:3:2
80 66 84 87 103
233
93.3
0.35
2000:1:2:3:3
80 90 123 129 140
230
95.3
0.28
2000:1:2:3:3
80 114
136 140 159
232
-- --
__________________________________________________________________________
EXAMPLES 12-13
In Examples 12 and 13 various activators are used instead of the
tributyltin hydride used in the previous examples. Among the activators
tested were triphenyltin hydride (Ph.sub.3 SnH), diethylaluminum chloride
(Et.sub.2 AlCl), diethylzinc (DEZ), diisobutylzinc (DIBZ), and
ethyl-n-propoxyaluminum chloride (Et(n-Pro)AlCl) (ENPAC). Example 12
employed the diisopropyl substituted tungsten compound of Example 1, and
in Table 9 are seen the activators that worked to polymerize the DCPD
monomer.
In Example 13 the tungsten compound of Example 3 was used with various
activator compounds. Table 10 shows the results of DCPD polymerization
with such activators.
EXAMPLE 14
Polymerization of dicyclopentadiene was completed utilizing WOCl.sub.3
(OAr) catalysts and n-Bu.sub.3 SnH. The WOCl.sub.3 (OAr) catalysts were
prepared in accordance with the general procedure of Example 2.
EXAMPLES 15-16
In Examples 15 and 16 the activator used was a mixture of tri-n-butyltin
hydride and triethylsilane (Et.sub.3 SiH). The tungsten compound of
Example 1 was used in the polymerizations of Example 15, the results of
which are shown in Table 11. The tungsten compound of Example 3 was used
in the polymerizations of Example 16, the results of which are shown in
Table 12.
TABLE 9
__________________________________________________________________________
DCPD Polymerization Utilizing Various Activators In Combination with
WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:AC
Activator
(.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:3:
n-Bu.sub.3 SnH*
30 7 23 28 41 206
75.9
0.35
2000:1:2:3:
n-Bu.sub.3 SnH*
80 9 24 30 45 211
95.5
0.33
2000:1:2:3:
Ph.sub.3 SnH
30 1 27 31 48 210
65.6
0.28
2000:1:2:3:
Ph.sub.3 SnH
80 1 26 30 45 214
76.1
0.73
2000:1:2:3:
Ph.sub.3 SnH*
80 40 79 84 98 229
83.7
0.58
2000:1:2:3:
Et.sub.2 AlCl
30 1 160 169 190
193
58.1
0.55
2000:1:2:3:
Et.sub.2 AlCl
80 2 44 47 61 220
-- --
2000:1:2:3:
Et.sub.2 AlCl**
80 16 147 159 168
212
69.3
2.04
2000:1:2:3:
DIBZ**
80 25 1.5 245 260
196
92.9
1.71
__________________________________________________________________________
*Addition of one mole equivalent of tributylphosphite (TBP) per mole of
activator.
**Addition of one mole equivalent of diglyme (DG) per mole of activator.
TABLE 10
__________________________________________________________________________
DCPD Polymerization Utilizing Various Activators In Combination with
WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
DCPD:W:DG:AC
Activator
(.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
2000:1:2:3:
n-Bu.sub.3 SnH*
30 7 19 25 41 209
94.1
0.12
2000:1:2:3:
n-Bu.sub.3 SnH*
80 4 18 24 39 209
82.1
0.20
2000:1:2:3:
Ph.sub.3 SnH
30 1 74 85 99 200
-- --
2000:1:2:3:
Ph.sub.3 SnH
80 1 30 34 48 214
110.0
0.27
2000:1:2:3:
Ph.sub.3 SnH*
80 72 172 182 200
222
114.9
1.10
2000:1:2:3:
Et.sub.2 AlCl**
30 12 104 114 130
202
67.7
1.8
2000:1:2:3:
Et.sub.2 AlCl**
80 9 35 39 48 207
89.1
2.9
2000:1:2:3:
ENPAC 80 90 279 282 300
239
126.1
0.41
2000:1:2:3:
DEZ** 25 1 7 13 23 193
-- --
2000:1:2:3:
DIBZ**
30 1 19 25 36 205
-- --
2000:1:2:3:
DIBZ**
28 1 29 33 50 208
-- --
2000:1:2:3:
DIBZ**
80 1 24 27 46 209
-- --
__________________________________________________________________________
*Addition of one mole equivalent of tributylphosphite (TBP) per mole of
activator.
**Addition of one mole equivalent of diglyme (DG) per mole of activator.
TABLE 11
__________________________________________________________________________
Reactivity of WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.2 with
Different Ratios
of Tri-n-Butyltin Hydride and Triethylsilane
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
Activator (.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
75% n-Bu.sub.3 SnH: 25% Et.sub.3 SiH
30 12 33 37 53 209
104.1
0.09
75% n-Bu.sub.3 SnH: 25% Et.sub.3 SiH
80 9 24 28 44 215
105.6
0.28
50% n-Bu.sub.3 SnH: 50% Et.sub.3 SiH
30 15 58 64 80 202
87.1
0.11
50% n-Bu.sub.3 SnH: 50% Et.sub.3 SiH
80 11 27 31 46 213
93.8
0.31
25% n-Bu.sub.3 SnH: 75% Et.sub.3 SiH
30 28 -- -- 300
56
-- --
25% n-Bu.sub.3 SnH: 75% Et.sub.3 SiH
80 15 -- -- 300
88
-- --
__________________________________________________________________________
TABLE 12
__________________________________________________________________________
Reactivity of WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2 with
Different Ratios
of Tri-n-Butyltin Hydride and Triethylsilane
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
Activator (.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
75% n-Bu.sub.3 SnH: 25% Et.sub.3 SiH
30 10 29 33 52 210
83.9
0.07
75% n-Bu.sub.3 SnH: 25% Et.sub.3 SiH
80 9 19 23 39 218
94.3
0.19
50% n-Bu.sub.3 SnH: 50% Et.sub.3 SiH
30 12 46 51 68 199
82.7
0.05
50% n-Bu.sub.3 SnH: 50% Et.sub.3 SiH
80 10 22 27 44 217
90.8
0.18
25% n-Bu.sub.3 SnH: 75% Et.sub.3 SiH
30 19 102 109 120
202
90.2
0.3
25% n-Bu.sub.3 SnH: 75% Et.sub.3 SiH
80 16 39 44 59 213
83.9
0.98
__________________________________________________________________________
EXAMPLES 17-18
WOCl.sub.2 (OAr).sub.2 catalysts were prepared in accordance with analogous
procedures to those disclosed in Example 3, substituting the appropriate
phenol for that disclosed in Example 3. The results of polymerization with
these catalysts is shown in Table 13.
WOCl.sub.3 (OAr) catalysts were prepared in accordance with analogous
procedures to those disclosed in Example 2. The results of polymerization
with these catalysts is shown in Table 14.
EXAMPLE 19
In examining the synthesis of WOCl.sub.2 (OC.sub.56 H.sub.3
-2,6-i-Pr.sub.2).sub.2 (Example 1), it was found that WOCl(OC.sub.6
H.sub.3 -2,6-i-Pr.sub.2).sub.3 can be generated in the reaction pot at
ambient temperature. Pure WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3 can
only be synthesized by the addition of one mol. equivalent of lithium
2,6-di-isopropylphenoxide in diethyl ether at 30.degree. C. At 80.degree.
C., WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3 can be activated by
tri-n-butyltin hydride (n-Bu.sub.3 SnH) to generate a polymerizing species
(Table 15). No polymerization exotherm was observed at room temperature.
The 2,6-dichlorophenol analog to the above 2,6-dichlorophenol substituted
tungsten compound WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3, was found to
be much more easily activated by n-Bu.sub.3 SnH, so polyDCPD was formed at
room temperature as well as at more typical molding temperatures.
TABLE 13
__________________________________________________________________________
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
Activator (.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
WOCl.sub.2 (OC.sub.6 H.sub.2 -2,4-Cl.sub.2 -6-Me).sub.2
31 11 24 33 51 196
64.2
0.44
WOCl.sub.2 (OC.sub.6 H.sub.2 -2,4-Cl.sub.2 -6-Me).sub.2
80 10 21 26 41 209
75.1
0.66
WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Ph.sub.2).sub.2
30 15 38 43 60 203
121.3
0.16
WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Ph.sub.2).sub.2
80 11 21 27 39 202
137.9
0.29
__________________________________________________________________________
The above polymerizations were run at the following ratios:
DCPD:W:DG:Sn:TBP
2000:1:2:3:3
TABLE 14
__________________________________________________________________________
Initial Residual
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
Swell
Monomer
Activator (.degree.C.)
(sec)
(sec)
(sec)
(sec)
(.degree.C.)
(%) (%)
__________________________________________________________________________
WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-Br.sub.2)
30 5 15 22 40 205
72.5
0.10
WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-Br.sub.2)
80 4 12 18 36 209
79.9
0.23
WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-OMe.sub.2)
31 40 84 89 105
208
68.5
0.28
WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-OMe.sub.2)
80 15 23 30 46 218
86.2
0.58
__________________________________________________________________________
The above polymerizations were run at the following ratios:
DCPD:W:DG:Sn:TBP
2000:1:2:3:3
TABLE 15
__________________________________________________________________________
Polymerization Data for WOCl(OAr).sub.3 /n-Bu.sub.3 SnH Mixtures:
Effect of Temperature and Rate Moderator
Initial
Temp.
t.sub.gel
t.sub.100.degree. C.
t.sub.180.degree. C.
tT.sub.max
T.sub.max
WOCl(OAr).sub.3 Catalyst
W:Sn:TBP
(.degree.C.)
(Sec)
(sec)
(sec)
(sec)
(.degree.C.)
__________________________________________________________________________
WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3
1:3:0 31 1 no polymerization at 420s
WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3
1:3:0 80 1 224 231 243
214
WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3
1:3:0 80 1 211 219 239
225
WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3
1:3:0 31 1 23 27 42 205
WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3
1:3:0 31 1 29 37 53 206
WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3
1:3:0 80 1 21 29 41 201
WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3
1:3:0 80 1 22 29 42 194
WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3
1:3:3 80 11 96 105 115
214
WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3
1:3:3 80 13 87 93 107
221
WOCl(OC.sub.6 H.sub.3 -2,6-i-Pr.sub.2).sub.3
1:3:3 80 13 85 92 109
223
WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3
1:3:3 31 8 59 66 78 199
WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3
1:3:3 31 8 60 64 82 208
WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3
1:3:3 80 7 28 31 46 219
WOCl(OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.3
1:3:3 80 7 28 32 47 214
__________________________________________________________________________
Overall reaction ratio DCPD:W procatalyst:diglyme:nBu.sub.3 SnH =
2000:1:2:3)
EXAMPLE 20
In this example, the tungsten catalyst compositions of Examples 1-4 were
used to mold 98-99% pure DCPD in combination with tri-n-butyltin hydride,
moderated by tributylphosphite in a 3.5% Royalene 301T (ethylene propylene
diene monomer (EPDM)) rubberized formulation. When the catalyst of Example
1 was used, parts were produced with 1.2% residual monomer. The reaction
ratio was DCPD:W:DG:n-Bu.sub.3 SnH:TBP = 2000:1:2:3:2. The properties were
comparable to prior art formulations, except that the heat distortion
temperature (HDT) was significantly higher than has been found except when
a quantity of tricyclopentadiene or some other monomers were added to the
DCPD monomer. The HDT was found to be about 117.degree.-118.degree. C.,
more than 15.degree. C. than the control. The addition of the antioxidant
Irganox 1035 did not affect the Notched Izod value, but reduced the heat
distortion temperature by about 6.degree. C. The addition of 10% of
tricyclopentadiene (Cp trimer) to the formulation resulted in a further
8.degree. C. boost in HDT. More importantly, the Notched Izod value
remained high compared to prior art compositions, even after aging. A
sample of this rubberized material, containing no antioxidant, was aged at
70.degree. C. and the change in Notched Izod as a function of time was
recorded. After four days, the notched izod had plateaued at about 5.0 ft.
lb./in. as compared to prior art material which had a Notched Izod value
of about 2.5 ft lb/in after aging.
A pure tungsten catalyst having the formula WOCl.sub.2 (OC.sub.6 H.sub.3
-2,6-Cl.sub.2).sub.2 was prepared in accordance with the procedure of
Example 3 and when activated by tri-n-butyltin hydride an extremely active
catalyst solution was produced for the polymerization of
dicyclopentadiene. At 80/60.degree. C. molding temperatures, a 3.5%
Royalene 301T rubberized DCPD solution (DCPD:W:Sn = 2000:1:3) was
polymerized by WOCl.sub.2 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2).sub.2
(stabilized by two molar equivalents of diglyme) in combination with
n-Bu.sub.3 SnH (moderated by two equivalents of tributylphosphite (TBP))
to yield poly(DCPD) containing only 0.37% residual DCPD and having a high
heat distortion temperature of 118.degree. C.
WOCl.sub.3 (OC.sub.6 H.sub.3 -2,6-Cl.sub.2) was prepared in accordance with
the procedure of Example 2. The catalyst system produced was very fast in
gelling and curing DCPD. For example, at proportions of
DCPD:W:DG:n-Bu.sub.3 SnH:TBP of 2000:1:2:3:3 at 30.degree. C., t.sub.gel
was less than 1 second, t.sub.100.degree. C. was 4 seconds and
t.sub.180.degree. C. was 10 seconds. It was found possible to prepare
polyDCPD plaques having very low levels of residual monomer (0.28%) and
excellent properties (Table 13). The heat distortion temperature of
123.degree. C. is a very high level. Table 16 shows the properties of
parts molded in accordance with the above description.
TABLE 16
__________________________________________________________________________
Tensile Flex HDT Residual
Tg
Modulus
Strength
Elongation
Modulus
Strength
Notched Izod
(264 psi)
Monomer
(DMA)
Sample (Kpsi)
(Kpsi)
(%) (Kpsi)
(Kpsi)
(ftlb/in)
(.degree.C.)
(wt %)
(.degree.C.)
__________________________________________________________________________
Example 1 Catalyst
249.0
5.5 28.0 277.4
9.8 11.7 117 1.2 154
(2 eq. DG/2 eq. TBP)
Example 1 Catalyst
-- -- -- -- -- 11.7 111 0.86 --
(2 eq. DG/2 eq. TBP)
2% Irganox 1035
Example 1 Catalyst
237.6
5.9 37.9 283.1
9.8 7.6 125 1.3 165
(2 eq. DG/2 eq. TBP)
10% Cp-trimer Monomer
Example 3 Catalyst
237.6
5.9 37.1 252.0
8.9 9.1 118 0.38 148
(2 eq. DG/2 eq. TBP)
Example 3 Catalyst
250.4
6.7 66.6 280.3
10.0 9.1 123 0.28 146
(2 eq. DG/2 eq. TBP)
__________________________________________________________________________
In all cases, reaction ratio used is DCPD:W:Sn = 2000:1:3.
Diglyme (DG) is added as a catlyst stabilizer. Tributylphosphite (TBP) is
added as a rate modifier.
Top